E 75 76 (2004)

Designation E 75 – 76 (Reapproved 2004) Standard Test Methods for Chemical Analysis of Copper Nickel and Copper Nickel Zinc Alloys1 This standard is issued under the fixed designation E 75; the number[.]

Designation: E 75 – 76 (Reapproved 2004) Standard Test Methods for Chemical Analysis of Copper-Nickel and Copper-Nickel-Zinc Alloys1 This standard is issued under the fixed designation E 75; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision A number in parentheses indicates the year of last reapproval A superscript epsilon (e) indicates an editorial change since the last revision or reapproval Scope 1.1 These test methods cover procedures for the chemical analysis of copper-nickel and copper-nickel-zinc alloys having chemical compositions within the following limits:2 Element Copper NickelA ZincB Lead Tin Iron Manganese Cobalt Periodate (Photometric) Method Nickel by the Dimethylglyoxime Method Tin by the Iodimetric Titration Method Zinc by the Oxide or Ferrocyanide Method Concentration Range,% 40 and over 10 to 50 to 40 to 15 to 10 0.00 to 0.00 to 0.00 to 0.5 2a 2b 2a 1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use For precautions to be observed in these test methods, refer to Practices E 50 Referenced Documents 2.1 ASTM Standards: E 29 Practice for Using Significant Digits in Test Data to Determine Conformance With Specifications E 50 Practices for Apparatus, Reagents, and Safety Precautions for Chemical Analysis of Metals E 55 Practice for Sampling Wrought Nonferrous Metals and Alloys for Determination of Chemical Composition E 60 Practice for Photometric and Spectrophotometric Methods for Chemical Analysis of Metals E 88 Practice for Sampling Nonferrous Metals and Alloys in Cast Form for Determination of Chemical Composition A Includes cobalt In the case of copper-base alloys containing % and over of zinc, the zinc is usually calculated by difference B Whenever possible the technique and procedures for analysis should be checked against a National Institute of Standards and Technology standard sample having a composition comparable to the material being analyzed 1.2 The test methods appear in the following order: Sections Cobalt: Alpha-Nitroso-Beta-Naphthol Method Nitroso-R-Salt (Photometric) Method Copper, or Copper and Lead Simultaneously, by the Electrolytic Method Iron: Dichromate Method Thiocyanate (Photometric) Method Salicylate (Photometric) Method Lead: Electrolytic Method Sulfate Method Manganese: Persulfate Method Sections 59 to 66 26 to 28 29 to 37 2a 38 to 40 Significance and Use 3.1 These test methods for the chemical analysis of metals and alloys are primarily intended to test such materials for compliance with compositional specifications It is assumed that all who use these test methods will be trained analysts capable of performing common laboratory procedures skillfully and safely It is expected that work will be performed in a properly equipped laboratory 2a 2a 12 to 15 2b 2b Apparatus and Reagents 4.1 Apparatus and reagents required for each determination are listed in separate sections preceding the procedure The apparatus, standard solutions, and certain other reagents used These test methods are under the jurisdiction of ASTM Committee E01 on Analytical Chemistry for Metals, Ores, and Related Materials and are the direct responsibility of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, their Alloys and Related Metals Current edition approved June 1, 2004 Published August 2004 Originally approved in 1950 Last previous edition approved in 1996 as E75 – 76 (1996) For procedures for the chemical analysis of nickel-copper alloys containing 50 % and over of nickel, see ASTM Methods E 76, for Chemical Analysis of Nickel-Copper Alloys, Annual Book of ASTM Standards, Vol 03.05 2a Discontinued as of June 30, 1975 2b Discontinued Aug 27, 1976 For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org For Annual Book of ASTM Standards volume information, refer to the standard’s Document Summary page on the ASTM website Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States E 75 – 76 (2004) in more than one procedure are referred to by number and shall conform to the requirements prescribed in Practices E 50, except that photometers shall conform to the requirements prescribed in Practice E 60 as necessary, and finally evaporate to fumes Transfer the digested solution to a 400-mL beaker and dilute to 250 mL Add NaOH solution until the solution is alkaline and the tin hydroxide has dissolved Add 20 mL of Na2S solution (250 g Na2S/L), stir thoroughly, and digest on the steam bath for several hours, or until the supernatant liquid is clear Cool to room temperature, filter through a fine paper, and wash the precipitate with Na2S solution (20 g Na2S/L) Dissolve the residue in a few millilitres of HNO3 (1 + 1), neutralize with NH4OH, and redissolve any precipitate with a minimum of HNO (1 + 1) Combine with the reserved filtrate (10.2) and continue in accordance with 10.5 10.4 An alternative method for recovering copper and lead is to return the metastannic acid and paper obtained as described in 10.2 to the original beaker, add 15 to 20 mL of HNO3 and 10 to 15 mL of HClO4, heat to copious white fumes, and boil to destroy organic matter Cool, wash the cover glass and sides of the beaker, and add 15 to 25 mL of HBr Heat to copious white fumes to volatilize the tin If the solution is not clear, repeat the treatment with HBr Evaporate the solution to near dryness, cool, and dissolve the residue in a few millilitres of water Combine with the reserved filtrate (10.2) and continue in accordance with 10.5 10.5 Add drop of HCl (1 + 99) and mL of sulfamic acid solution and dilute to 150 mL Insert the electrodes into the solution, cover with a pair of split watch glasses, and electrolyze overnight at a current density of 0.5 A/dm2 or for a short period at a current density of A/dm2(Note 3) The more rapid procedure requires the use of gauze cathodes After the blue color of the copper has disappeared, wash down the cover glasses, electrodes, and sides of the beaker, and continue the electrolysis until deposition of the copper is complete, as indicated by failure to plate on a new surface when the level of the solution is raised When no copper appears, it can be assumed that all the lead also has been deposited (Note 4) Reserve the electrolyte Photometric Practice 5.1 Photometric practice prescribed in these methods shall conform to Practice E 60 Sampling 6.1 Wrought products shall be sampled in accordance with Practice E 55 Cast products shall be sampled in accordance with Practice E 88 Rounding Calculated Values 7.1 Calculated values shall be rounded to the desired number of places in accordance with the rounding method given in 3.4 and 3.5 of Practice E 29 COPPER, OR COPPER AND LEAD SIMULTANEOUSLY, BY THE ELECTROLYTIC TEST METHOD (This test method, which consisted of Sections 8-11 of this standard, was discontinued in 1975.) NOTE 1—Sections 8-11 of this standard were removed as a part of the revision of E75 approved June 30, 1975 Since they are no longer an approved part of this standard, the sections are included here for reference purposes only Subcommittee E03.05 is in the process of updating these methods Apparatus 8.1 Electrodes for Electroanalysis— Apparatus No 9 Reagents 9.1 Sodium Hydroxide Solution (250 g NaOH/L) 9.2 Sodium Sulfide Solution (250 g Na2S/L) 9.3 Sodium Sulfide Solution (20 g Na2S/L) 9.4 Sulfamic Acid Solution (100 g/L) NOTE 3—When agitation of the electrolyte is permissible in order to decrease the time of deposition, one of the types of rotating forms of electrodes generally available may be employed NOTE 4—If the electrolyte is not to be used for subsequent determinations, remove a few drops of the solution, place on a porcelain spot plate, and treat with saturated H2S solution Continue electrolysis until no CuS precipitate is observed 10 Procedure for Alloys Containing Under % of Lead NOTE 2—If more than % of lead is present, the copper only shall be determined by this procedure as the anode deposit is not sufficiently adherent for safe handling The lead shall then be determined on a separate sample as described in the sulfate method, Sections 16 and 17 10.6 When deposition of the copper is complete, with the current still on, lower the beaker slowly, while washing the cathode with water Remove the cathode, rinse it in water, and dip it in two successive baths of ethanol or methanol Dry in an oven at 110°C for to min, cool, and weigh the deposit as metallic copper 10.7 If lead is being determined, remove the anode, rinse thoroughly with water, and dry at 110 to 120°C for 30 The deposit is fragile and must be handled carefully Cool the anode and weigh the deposit 10.8 Correction must be made for manganese, which is frequently present in these alloys and some of which may codeposit with the lead Place the anode in a 150-mL beaker and dissolve the deposit in 20 mL of HNO3 (1 + 1) and mL of H2O (3 %) Remove the anode and wash with water Add 10.1 Transfer 2.0000 g of the sample to a 250-mL beaker, cover, and dissolve in 25 mL of HNO3(1 + 1) When dissolution is complete, boil gently to expel brown fumes Add 50 mL of hot water and observe the clarity of the solution If the solution is clear, proceed as described in 10.5 If enough tin is present at this point to form a cloud, proceed as described in 10.2 and 10.3 or 10.2 and 10.4 10.2 Allow to stand on a steam bath for h or until the precipitate has coagulated Add paper pulp and filter off the metastannic acid through a fine paper into a 250-mL beaker Wash several times with hot HNO3 (1 + 99) and reserve the filtrate and washings 10.3 Transfer the filter paper and contents to the original beaker and add 15 mL of H2SO4 and 15 mL of HNO Heat until all organic matter is decomposed, adding additional HNO E 75 – 76 (2004) 13.5 Correct for manganese and calculate the percentage of lead in accordance with 10.8 and 10.9 mL of H 3PO4 and boil for to 10 Determine manganese either photometrically by the periodate method (Sections 31–38) or volumetrically by the persulfate method (Sections 56 to 58) 10.9 Calculation—Calculate the percentages of copper and lead as follows: 14 Procedure for Alloys Containing 0.05 % and Over of Tin 14.1 Proceed in accordance with 13.1 or 13.2 Remove tin in accordance with 10.2 and 10.3 or 10.2 and 10.4 Electrolyze and determine lead as directed in 13.3-13.5 Copper, % ~A/B! 100 Lead, % ~@~C 1.58 D! 0.866]/B! 100 where: A = grams B = grams C = grams D = grams of of of of 15 Precision and Bias 15.1 This test method was originally approved for publication before the inclusion of precision and accuracy statements within standards was mandated The original interlaboratory test data is no longer available The user is cautioned to verify by the use of reference materials, if available, that the precision and accuracy of this method is adequate for the contemplated use copper, sample used, combined deposit of PbO2 plus MnO2, and manganese 11 Precision and Bias 11.1 This method was originally approved for publication before the inclusion of precision and accuracy statements within standards was mandated The original interlaboratory test data is no longer available The user is cautioned to verify by the use of reference materials, if available, that the precision and accuracy of this method is adequate for the contemplated use LEAD BY THE SULFATE TEST METHOD (This test method, which consisted of Sections 16 and 17, was discontinued in 1976.) TIN BY THE IODOMETRIC TITRATION TEST METHOD (This test method, which consisted of Sections 18 through 20, was discontinued in 1976.) LEAD BY THE ELECTROLYTIC TEST METHOD 12 Apparatus 12.1 Electrodes for Electroanalysis— Apparatus No Use the larger electrode as the anode ZINC BY THE OXIDE OR FERROCYANIDE TEST METHOD (This test method, which consisted of Sections 21 and 22 of this standard, was discontinued in 1975.) 13 Procedure for Alloys Containing Under 0.05 % of Tin 13.1 Solution of Samples Containing Under 0.1 % of Lead—Transfer 10 g of the sample to a 400-mL beaker, cover, and dissolve in 60 mL of HNO3 (1 + 1) When dissolution is complete, boil gently to expel brown fumes Wash down the cover glass and the sides of the beaker and dilute to 250 mL 13.2 Solution of Samples Containing 0.1 to % of Lead (see Note 2)— Transfer 1.000 g of the sample to a 250-mL beaker, cover, and dissolve in 20 mL of HNO3 (1 + 1) When dissolution is complete, boil gently to expel brown fumes Wash down the cover glass and the sides of the beaker and dilute to 150 mL 13.3 Insert the electrodes into the solution, cover with a pair of split watch glasses, and electrolyze for h at a current density of 1.25 to 1.50 A/dm2 It is preferable to agitate the electrolyte Electrolysis may take place overnight without agitation and using a lower current density Wash down the cover glasses, electrodes, and sides of the beaker, and continue the electrolysis until no darkening of the newly exposed surface of the platinum anode can be detected when the current has been continued for 15 after the level of the liquid was raised 13.4 When deposition of the lead is complete, without interrupting the current, siphon off the electrolyte, at the same time filling the beaker with water Remove the anode quickly, rinse thoroughly with water, and dry at 110 to 120°C for 30 The deposit is fragile and must be handled carefully Cool the anode and weigh the deposit NICKEL BY THE DIMETHYLGLYOXIME TEST METHOD (This test method, which consisted of Sections 23 through 25 of this standard, was discontinued in 1975.) COBALT BY THE ALPHA-NITROSO-BETA-NAPHTHOL TEST METHOD 26 Reagents 26.1 Alpha-Nitroso-Beta-Naphthol Solution (70 g/L)— Dissolve g of alpha-nitroso-beta-naphthol in 100 mL of glacial acetic acid and filter the solution Prepare this reagent as required just before using 26.2 Zinc Oxide Suspension—Transfer 300 mL of water and 50 g of finely powdered ZnO to a 500-mL flask Stopper the flask and shake the mixture vigorously each time before using 27 Procedure 27.1 Transfer g of the sample to a 250-mL beaker and dissolve in 40 mL of HNO3 (1 + 1) When dissolution is complete, boil gently to expel brown fumes If a precipitate of tin is present, add 50 mL of hot water, heat on the steam bath for h, and filter off the metastannic acid through a fine paper, washing thoroughly with hot HNO3 (1 + 99) 27.2 Remove the copper and lead in accordance with 10.5 E 75 – 76 (2004) fering complexes and stabilizes the cobalt complex Photometric measurement is made at approximately 520 nm 27.3 Evaporate the electrolyte to a thick syrup, and convert the nitrates to chlorides by two evaporations to dryness with 25-mL portions of HCl Cool, add 100 mL of HCl (1 + 19), and heat until the salts are dissolved Transfer to a 500-mL Erlenmeyer flask and dilute to 250 mL 27.4 Heat to 60 to 80°C, swirl vigorously, and add ZnO suspension in small increments until an excess of ZnO is present The presence of excess ZnO is indicated by a milky turbidity in the supernatant liquid and white particles on the bottom of the flask on standing Heat on a steam bath for 15 and filter through a medium paper into a 600-mL beaker Wash the residue with hot water and discard it Add 20 mL of HCl to the filtrate and adjust the volume to 400 mL 27.5 Heat the solution to 60°C, add 15 mL of alpha-nitrosobeta-naphthol solution, and stir vigorously for Cool to room temperature, and stir occasionally for h Filter through a medium, ashless paper, wash thoroughly with hot HCl (1 + 19), and finally with hot water 27.6 Ignite the precipitate in a 30-mL, tall-form porcelain crucible Allow the crucible to cool, add to g of Na2S2O 7, and heat on a hot plate until dense white fumes appear Fuse until the oxides are dissolved, allow to cool, tap gently to detach the melt, and transfer it to a 400-mL beaker Rinse the crucible thoroughly with hot water, and add the rinsings to the beaker Heat gently until the melt dissolves, add 10 mL of HCl, and dilute to 200 mL Reprecipitate, filter, and wash as described in 27.5 27.7 Ignite the reprecipitated cobalt in a tared porcelain crucible at 750 to 850°C to constant weight Cool in a desiccator and weigh as Co3O4 27.8 Blank—Make a blank determination, following the same procedure and using the same amounts of all reagents 27.9 Calculation—Calculate the percentage of cobalt as follows: 30 Concentration Range 30.1 The recommended concentration range is from 0.005 to 0.10 mg of cobalt in 50 mL of solution, using a cell depth of cm.4 31 Stability of Color 31.1 The color is stable for more than h 32 Interfering Elements 32.1 Provision is made in the procedure for preventing, or compensating for, interference from metals present in the maximum limits given in 1.1 33 Apparatus 33.1 Electrodes for Electroanalysis—Apparatus No 34 Reagents 34.1 Cobalt Standard Solution (1 mL = 0.01 mg Co)— Dissolve 0.1000 g of pure cobalt metal (Note 5) in about 10 mL of HNO3 (1 + 1) Boil to expel brown fumes Cool and dilute to L in a volumetric flask and mix Dilute 100 mL of this solution to L in a volumetric flask and mix NOTE 5—Alternatively, the solution may be prepared as follows: Dissolve 0.4770 g of CoSO4·7H2O in about 75 mL of water, add mL of H2SO4, dilute to L in a volumetric flask, and mix Standardize the solution as follows: Transfer a 100-mL aliquot to a 400-mL beaker, add 10 mL of HCl, and dilute to 200 mL Proceed in accordance with 27.5 and 27.7 For use, dilute 100 mL of this standardized solution to L in a volumetric flask and mix 34.2 Nitroso-R-Salt Solution (7.5 g/L)—Dissolve 0.75 g of nitroso-R-salt in water and dilute to 100 mL 34.3 Sodium Acetate Solution (500 g/L)—Dissolve 500 g of NaC2H3O 2·3H2O in about 600 mL of water and dilute to L Cobalt, % ~@~A B! 0.734]/C! 100 where: A = grams of Co3O4 in sample, B = correction for blank, g, and C = grams of sample used 35 Preparation of Calibration Curve 35.1 Transfer 1.0, 2.0, 4.0, 6.0, 8.0, and 10.0-mL aliquots of standard cobalt solution to 50-mL volumetric flasks and dilute to 10 mL Add 10 mL of water to an additional 50-mL volumetric flask and carry through as a reagent blank 35.2 Add to each flask, in the order given, mL of sodium acetate solution and 2.0 mL of nitroso-R-salt solution, mixing between additions (Note 6) Add a glass bead, heat to boiling, and maintain just under the boiling temperature for to Add 5.0 mL of HNO3 (1 + 2) and boil gently for to Cool to room temperature, dilute to the mark, and mix 28 Precision and Bias 28.1 This test method was originally approved for publication before the inclusion of precision and accuracy statements within standards was mandated The original interlaboratory test data is no longer available The user is cautioned to verify by the use of reference materials, if available, that the precision and accuracy of this test method is adequate for the contemplated use NOTE 6—The pH of the solutions at this point should be about 5.5 35.3 Transfer a suitable portion of each solution to an absorption cell and measure the transmittance or absorbance against the blank at approximately 520 nm COBALT BY THE NITROSO-R-SALT (PHOTOMETRIC) TEST METHOD 29 Summary of Test Method 29.1 Cobalt, in a hot solution buffered with sodium acetate, forms an orange-colored complex with nitroso-R-salt The addition of a controlled amount of nitric acid destroys inter- This procedure has been written for a cell having a 2-cm light path Cells having other dimensions may be used, provided suitable adjustments can be made in the amounts of sample and reagents used E 75 – 76 (2004) room temperature More water may be added from time to time as long as crystals remain undissolved 38.3 Potassium Dichromate Standard Solution (0.05 N)— Reagent No 10 38.4 Sodium Diphenylamine Sulfonate Indicator Solution (2 g/L) 38.5 Stannous Chloride Solution (42 g SnCl 2/L)—Dissolve 12.5 g of SnCl2·2H 2O in 25 mL of HCl, and dilute to 250 mL Keep the solution in a well-stoppered bottle 35.4 Plot the values obtained against milligrams of cobalt per 50 mL of solution 36 Procedure 36.1 If the electrolyte, or an aliquot of it, reserved in accordance with 10.5 is available, proceed as directed in 36.2 If the electrolyte is not available, transfer 2.00 g of the sample to a 250-mL beaker Dissolve the sample and remove copper, lead, and tin in accordance with 10.1-10.5 Carry a blank through all steps of the procedure 36.2 Transfer the electrolyte or aliquot of it, reserved in accordance with 10.5 or obtained in accordance with 36.1, to a 200-mL volumetric flask, dilute to the mark, and mix Transfer two equal aliquots (not exceeding 5.0 mL) containing under 0.10 mg of cobalt (preferably about 0.075 mg) to 50-mL volumetric flasks and dilute to 10 mL Proceed in accordance with 35.2, except to omit the addition of nitroso-R-salt to one of the aliquots Treat similar aliquots of the blank solution in the same way 36.3 Transfer a suitable portion of each solution to an absorption cell and measure the transmittance or absorbance, at approximately 520 nm, of the solutions containing the cobalt complex against the corresponding solutions in which the cobalt complex was not developed 36.4 Using the value obtained, read from the calibration curve the number of milligrams of cobalt present in 50 mL of the final solution 36.5 Calculation—Calculate the percentage of cobalt as follows: 39 Procedure 39.1 If the iron content is under 0.25 %, transfer 5.0 g of the sample, from which adventitious iron has been removed, to a 400-mL beaker and dissolve in 50 mL of HNO3 (1 + 1) If the iron content is 0.25 % or over, transfer 1.00 to 2.00 g of the sample, from which adventitious iron has been removed, to a 250-mL beaker and dissolve in 25 mL of HNO3 (1 + 1) When dissolution is complete, boil gently to expel brown fumes Add 50 mL of hot water and observe the clarity of the solution If the solution is clear, proceed, as directed in 39.2 If enough tin is present to form a cloud, proceed in accordance with 10.2 and 10.3 or 10.3 and 10.4 to remove the tin and recover the iron in the metastannic acid precipitate before continuing in accordance with 39.2 of this section 39.2 Dilute the solution from 150 to 200 mL and add g of NH4Cl Add NH4OH (1 + 1) until the basic salts of copper and nickel are dissolved and the solution is deep blue in color; then boil gently for a few minutes Allow the precipitate to settle for a few minutes, and filter while hot, using a medium paper Wash the beaker and precipitate, first with hot NH4Cl wash solution, and finally with hot water to remove most of the soluble salts Place the original beaker under the funnel and dissolve the precipitate through the paper with 20 mL of hot HCl (1 + 1) to which has been added mL of H2O (3 %) Add the HCl in several portions, washing alternately with hot water Finally, wash thoroughly with hot water 39.3 Reprecipitate the iron, wash, and dissolve as described in 39.2 39.4 Evaporate the solution from 10 to 12 mL and wash down the sides of the beaker Heat to boiling and add SnCl2 solution dropwise, while swirling the beaker over a white background, until the yellow color of the FeCl3 disappears The sample must be kept near boiling for the entire period of reduction Add drops of SnCl2 solution in excess but no more 39.5 Dilute the reduced solution to 50 mL and cool to room temperature While stirring, add at one stroke 10 mL of a saturated solution of HgCl The resultant precipitate should be pure white in color, and in amount should be preferably not more than enough to give a pearly opalescence If the precipitate is gray or dark, too large an excess of SnCl2 has been used and it will be necessary to discard the solution and start anew To the properly reduced solution, add 10 mL of H3PO4 (1 + 3) and drops of sodium diphenylamine sulfonate indicator solution Cobalt, % ~A B!/~C 10! where: A = milligrams of cobalt found in 50 mL of the final solution, B = correction for the reagent blank, in milligrams of cobalt, and C = grams of sample represented in 50 mL of the final solution 37 Precision and Bias 37.1 This test method was originally approved for publication before the inclusion of precision and accuracy statements within standards was mandated The original interlaboratory test data is no longer available The user is cautioned to verify by the use of reference materials, if available, that the precision and accuracy of this test method is adequate for the contemplated use IRON BY THE DICHROMATE TEST METHOD 38 Reagents 38.1 Ammonium Chloride Wash Solution—Dissolve 20 g of NH4Cl in L of water made slightly alkaline with a few drops of NH4OH 38.2 Mercuric Chloride Solution—(Saturated)—Add 60 to 100 g of HgCl2 to 400 mL of hot water, shake, and cool to E 75 – 76 (2004) of cm.4 39.6 While stirring constantly, titrate slowly with K2Cr 2O7 solution until the color of the solution changes from green to a gray-green Continue the titration dropwise until the first tinge of purple or violet-blue appears 39.7 Blank—Make a blank determination, following the same procedure and using the same amounts of all reagents 61 Stability of Color 61.1 The permanganate color is stable indefinitely if reducing agents are absent 62 Interfering Elements 62.1 Provision is made in the procedure for preventing, or compensating for, interference from metals present in the maximum limits given in 1.1 NOTE 7—Ferric iron must be present in the solution in order to obtain the purple or violet-blue end point color If the color fails to form, the blank is less than the equivalent of drop of 0.02 N FeSO solution as this contains sufficient iron to yield an end point 39.8 Calculation—Calculate the percentage of iron as follows: 63 Reagents 63.1 Hydrobromic Acid-Bromine Mixture—Dilute 10 mL of bromine to 100 mL with HBr 63.2 Manganese Standard Solution (1 mL = 0.125 mg Mn)—Dissolve 0.3596 g of KMnO in about 100 mL of water Add 20 mL of H2SO4 (1 + 1) and transfer to a 1-L volumetric flask Add H2O2 (3 %) in small increments until the pink color of the permanganate is discharged Boil the solution gently for about 10 to destroy excess H2O2 Cool, dilute to the mark, and mix 63.3 Nitric-Phosphoric Acid Mixture—Mix 400 mL of water, 200 mL of HNO3, and 500 mL of H3PO 63.4 Potassium Periodate Solution (75 g KIO4/L)—Dissolve 1.0 g of urea in 100 mL of HNO3 (1 + 3) To this solution add 7.5 g of KIO and dissolve by shaking in a glass-stoppered bottle Iron, % ~@~A B!C 0.0559]/D! 100 where: A = millilitres of K2Cr2O7 solution required to titrate the sample, B = millilitres of K2Cr 2O7 solution required to titrate the blank, C = normality of the K2Cr2O7 solution, and D = grams of sample used 40 Precision and Bias 40.1 This test method was originally approved for publication before the inclusion of precision and accuracy statements within standards was mandated The original interlaboratory test data is no longer available The user is cautioned to verify by the use of reference materials, if available, that the precision and accuracy of this test method is adequate for the contemplated use 64 Preparation of Calibration Curve 64.1 Transfer 1.0, 2.0, 4.0, 6.0, 8.0, and 10.0-mL aliquots of standard manganese solution to 100-mL volumetric flasks Carry through an additional 100-mL volumetric flask for a reagent blank Add to each flask mL of H 3PO4 and dilute to about 50 mL 64.2 Add mL of KIO4 solution and a chip of silicon carbide Heat to boiling and boil gently for about Digest at slightly below boiling temperature for an additional 10 Cool to room temperature, dilute to the mark, and mix 64.3 Transfer a suitable portion of each solution to an absorption cell and measure the transmittance or absorbance against the blank at approximately 520 nm 64.4 Plot the values obtained against milligrams of manganese per 100 mL of solution IRON BY THE THIOCYANATE (PHOTOMETRIC) TEST METHOD (This test method, which consisted of Sections 41 through 48 of this standard, was discontinued in 1975.) IRON BY THE SALICYLATE (PHOTOMETRIC) TEST METHOD (This test method, which consisted of Sections 49 through 55 of this standard, was discontinued in 1975.) MANGANESE BY THE PERSULFATE TEST METHOD (This test method, which consisted of Sections 56 through 58, was discontinued in 1976.) 59 Summary of Test Method 59.1 Manganese in an acid solution is oxidized to permanganate by heating with potassium periodate Photometric measurement is made at approximately 520 nm 65 Procedure 65.1 If the tin content of the sample is such that there will be 50 mg or under of tin in the portion used, transfer 0.5 to 2.00 g of the sample, containing 0.12 to 12.5 mg of manganese, to a 150-mL beaker and dissolve in 25 mL of HNO3-H3PO4 mixture (Note 8) Carry a blank through all steps of the procedure When dissolution of the sample is complete, boil gently to expel brown fumes Cool, transfer to a 100-mL volumetric flask, dilute to the mark, and mix Continue in accordance with 65.3 60 Concentration Range 60.1 The recommended concentration range is from 0.06 to 1.25 mg of manganese in 100 mL of solution, using a cell depth NOTE 8—The H3PO4 contained in 25 mL of dissolving solution is sufficient to hold about 50 mg of tin in solution, provided the sample is not subjected to excessive boiling nor prolonged digestion For larger amounts of tin, proceed as directed in 65.2 MANGANESE BY THE PERIODATE (PHOTOMETRIC) TEST METHOD E 75 – 76 (2004) 65.2 If the tin content of the sample is such that there will be over 50 mg of tin in the portion used, transfer 0.5 to 2.00 g of the sample, containing 0.12 to 12.5 mg of manganese, to a 300-mL Erlenmeyer flask and dissolve in 15 to 25 mL of HBr-Br2 mixture Carry a blank through all steps of the procedure Add 10 mL of HClO4 and mL of H3PO 4, and heat to dense white fumes to volatilize the tin Cool and add 50 mL of water and mL of HNO3 Cool, transfer to a 100-mL volumetric flask, dilute to the mark, and mix Continue in accordance with 65.3 65.3 Transfer two equal aliquots containing under 1.25 mg of manganese (preferably about 0.75 mg) to 100-mL volumetric flasks Add sufficient H 3PO4 to bring the total content to mL (assuming that the content of H3PO4 in the original sample solution was 10 mL) and dilute to about 50 mL Treat similar aliquots of the blank solution in the same way 65.4 Proceed as directed in 64.2, except to omit the addition of KIO to one of the aliquots in each pair 65.5 Transfer a suitable portion of each solution to an absorption cell and measure the transmittance or absorbance of the solutions in which the permanganic acid color was developed against the corresponding solutions in which the color was not developed 65.6 Using the value obtained, read from the calibration curve the number of milligrams of manganese present in 100 mL of the final solution 65.7 Calculation—Calculate the percentage of manganese as follows: Manganese, % ~A B!/~C 10! where: A = milligrams of manganese found in 100 mL of the final solution, B = correction for the reagent blank, mg, of manganese, and C = grams of sample represented in 100 mL of the final solution 66 Precision and Bias 66.1 This test method was originally approved for publication before the inclusion of precision and accuracy statements within standards was mandated The original interlaboratory test data is no longer available The user is cautioned to verify by the use of reference materials, if available, that the precision and accuracy of this test method is adequate for the contemplated use ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and if not revised, either reapproved or withdrawn Your comments are invited either for revision of this standard or for additional standards and should be addressed to ASTM International Headquarters Your comments will receive careful consideration at a meeting of the responsible technical committee, which you may attend If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, at the address shown below This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website (www.astm.org)